TW200410926A - Novel thioether derivatives - Google Patents

Abstract

This invention provides a novel dendrimer compound for using as materials such as memory switch mechanism, which is immediately illuminated by light or electric energy. The dendrimer compound of this invention comprising the essential constitutive elements: unit 1 represented by the following formula: [wherein, ring A represents a homocyclic or heterocyclic 6-membered ring] to form the dendrimer structure and surface functional groups.

Description

200410926 (ii) Description of the invention: [Technical field to which the invention belongs] The present invention relates to novel thioether derivatives, methods for their production and uses, and particularly to sulfur-containing dendrimers and their synthetic intermediates. [Prior Art] Dendritic compounds have a specific polymer structure and can be expected to be used in a wide range of applications. Dendritic compounds have a dendritic structure consisting of a core (core) and regular orthodox branching units (Units), and a special chemical structure in which the functional groups arranged on the outermost layer are expanded in three dimensions, for example, in Nano (Science), Communication Science, Electronic Materials Science, Medicine, Pharmacy, Biology, Interface Science, Materials Science, etc. are being researched in various aspects ("Dendrite" issued by VCH Publishing Company in 1996 ( Dendritic Molecules), Modern Chemistry, June 1998, pp. 20-40, "Molecular Design of Dendrimers", "Multiple Functions of Dendrimers", ^ 47 4 11 ^ ^ (1998 Γ Application of Materials). Dendritic science appeared from about 1990 卞 Y Jun, the number of researches is increasing, and it can be said to be the latest science. ~ Do not use (Japanese Patent Application Laid-Open No. 33063 1), use of solar cells, electrophotographic photoreceptors (η ' δ71), the use of electronic materials (Japanese Patent Application ΐκΠΐ8, the use of crystals (Japanese Patent Application No. 2000264264), coatings, oil black square (Japanese Patent Application No. 1 1 -1 4 0 1 8 0), general φ With Dagger 4 Seven Teeth)! Use of flexible resin sheet (Special Umbrella) 1-3 2 3 3 2 4), Inspection of Cheng Dingwugu, [Use of Bismuth and Bali method (Special Kaiping 3H210D01 200410926 21 8494), Biosensor modifier The invention can be used in various industries such as Keiji Kaiping " ms. [Content of the invention] (Technical problem to be solved by the invention) The σ problem of this month is to provide a new dendritic compound with excellent functions. And the novel synthetic intermediates used in its manufacture. In the eighth edition, 0, right-handed fork light or electricity and other energy, the electrons existing in the structural part immediately flow to the core of insufficient electrons, which can make the core part first. Therefore, this The main object of the invention is to provide novel dendrimer compounds that can be used as electronic materials (such as memory switches). (Technical means to solve problems) In response to the above-mentioned problems, the inventors and others have intensively researched the results and successfully created The dendrimer northern compound containing a sulfur atom of the present invention. Furthermore, the present inventors have used the dendritic structure of the present invention by using a large amount of dendrimers Atoms, review the utilization of non-U sub \ orbital electrons. Therefore, it is learned that since the d_orbital electrons of sulfur atoms are more distant than the d_dominated electrons of oxygen atoms, free electrons are more active 'light or electric energy The electron from d • orbital can be easily transferred to the core of the electron-deficient structure. 'If the photoresist residue is caused by the core structure', the core part emits light by the transferred electron. Compared with the oxygen atom, the sulfur atom is dendritic. The structure and the core have greater polarizability. Due to Λ, the 2 dendrimer compounds of the present invention can be used as electronic materials (such as memory switches) for new knowledge. In addition, the present inventors also understood that the dendritic compound containing sulfur atoms 313210D01 6 200410926 may be deteriorated due to oxidation, but is formed on the opposite side of the dendrite to the outside of the main ridge (the opposite side of the core). The surface functional group can be used to form a dendrimer with a bulky substituent (which can combine dendrimers / increase the lifespan. U people note ~ large, and further, the present inventors understand the body It can be obtained from the specific synthesis history ... the novel synthesis of the dendritic structure of the human sulfur atom by the new structure. It is beneficial to the inventors in the industry to obtain so many to complete the present invention. Repeating the review, that is, the present invention is about: ⑴ "a dendritic compound, which is characterized by containing the following necessary constituent elements · core and unit 1 represented by the following formula:

S—— [In the formula, mounting A represents a pure carbon or a six-membered ring containing heteroatoms] The dendritic structure and surface functional groups formed. (2) A kind of dendritic compound 'characterized in that it is composed of a core, and the unit 1 described in the above (1) and the unit represented by the following formula: 〇—

[In the formula, ring A represents a pure carbon or a six-membered ring containing a hetero atom] or / and unit 3: 7 313210D01 200410926

——CH

[In the formula, ring A represents a pure carbon or a heteroatom-containing six-membered ring] A dendritic structure formed by a surface and a functional group on the surface.

(3) A dendritic compound characterized by a partial dendritic structure formed by a core and the unit 1 described in (1) above, a partial dendritic structure formed by the unit 2 described in (2) above, and (2) The dendritic structure of two or more partial dendritic structures in the Zoufen dendritic structure formed by unit 3 of the description, and the surface functional group. (1) The dendritic compound according to the above (2) or (2), characterized in that the number of levels of the dendritic structure is 2 to 10, and the dendritic structure is a level formed by the single A 1 described in the above (0). , And the hierarchy formed by the unit 2 described in the above ，, or / and the hierarchy formed by the unit 3 described in the above /. (5) The dendritic compound as described in the above-mentioned ⑴ to ⑷, characterized in that the unit A, unit 2 and unit 3 soil A is a benzene ring, D dense ring, or triple ring. (6) The dendritic compound as described in (1) to (5) above,-and eight are imitated as the surface, and this group is a substituted or unsubstituted alkyl group, a substituted fluorenyl group, or an alkoxy group. , Burning carboxyl, or fourth-grade money. (7) The dendritic compound as described in (6) above, ^ ^ _ can be used to test the surface function, which is characterized by the core, which is characterized by the core. (2) Cai Chouben (8) as described in (1) to (7) above. The dendrimer compound described in ()) is a chromophoric functional group. (9) The dendritic compound described in (1) to (7) above is based on Rhodamine pigment, quinazoline, 313210D01 8 200410926 (Perylene), azo compound, and 2,5-dihydroxy Residues of selected compounds from methyl benzoate, porphyrin, 4,4'-dihydroxybiphenyl, 1- (4,4,54 ,,-trihydroxyphenyl) ethane and coumarin derivatives. (10) —Sulfur compound represented by the following formula

[Wherein ring A is

A ring that is not a table, the position where the bonding bond extends has a substituent B, a substituent c, and a substituent D ′. The position other than the bonding bond of the above ring may be substituted, and the substituent B represents -S (〇) nR] {Formula Where η represents an integer from 0 to 2, R] represents a substituent}, substituent C represents x] R2 {wherein, χ] represents an intermediary group, R2 represents a substituent}, and substituent D represents a carbon atom and a ring A bound substituent]. (11) The sulfur compound according to the above (10), wherein R] and R2 are respectively the same or different metal detector, hydrogen atom, alkyl group, aralkyl group, amine group, or thio group which may be substituted Amine group. (12) The sulfur compound according to the above (10) or (11), wherein χ] is a fluorenylene group, a difluorenylene fluorenylene group, an oxygen atom, a sulfur atom, a maple or a sulfonic acid group. (13) The sulfur compound as described in any one of the above (10) to (12), wherein 9 313210D01 200410926 substituted D is cyano, fluorenyl or X2R3 [wherein, χ2 represents a substitutable Rhenylene,% or thiocarbonyl, and R3 represents a hydroxy, mercapto, or hydrazine group that can be protected (except for the case where X2 is a carbonyl group and R3 is a hydroxyl group). (14) 3,5-dimercaptobenzyl alcohol, ~ (15) 3,5-dimercaptobenzyl mercaptan, and (16) compounds represented by the following formula or their salts:

[Wherein R] and h each represent (1) an alkali metal such as sodium and potassium, (2) a hydrogen atom, (3) a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, or a thioalkoxy group, etc. Substituted alkoxy, (4) phenyl which may be substituted by the above-mentioned substituent, or (5) aralkyl which may be substituted by the above-mentioned substituent, (6) di-substituted amine or thio group represented by the following formula Amine group:

Z

II —c—n (r7) 2 (where R? Represents (1) an alkyl group which may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom, (2) a benzyl group which may be substituted with the above substituent, or (3) an aralkyl group which may be substituted by the above substituents, z represents an oxygen atom or a sulfur atom); η represents an integer of 0 to 2; does it mean an arylene group, a arylene group, an oxygen atom, or a sulfur atom? , Sulfonyl or sulfonate 10 313210D01 200410926 acid group; $ and l represent a hydrogen atom, (2) an alkyl group which may be substituted with a fluorine atom, a chlorine atom, and a halogen atom or a halogen atom, (3) an alkyl group which may be substituted with the above substituents Benzene, or (4) an aralkyl group which may be substituted by the above substituents, or may be combined to form a methine group, a keto group or a thioketone group. In addition, 4 丄 3 4 8 and h can also form cyano groups, the heart represents fluorenyl groups, (2) thio groups, (3) amine groups, (4) fluorenic acid groups, and fluorene can be replaced by atoms, chlorine atoms, and (6) an alkoxy group which may be substituted by the above substituent, or a thioloxy group which may be substituted by the above substituent, a phenyl group which may be substituted by the above substituent, Or (9) an aralkyl group which may be substituted by the above-mentioned substituents; and R6 means hydrogen, vial, alkyl, alkoxy, alkylthio, nitro, ethyl, monomethylamino, or diethylamine base]. [Embodiment] Definitions of terms used in the present invention are as follows. The calcined base may be linear or split, and the number of carbon atoms to 6 is preferred. The alkoxy group may be linear or branched, and a carbon number of liL 6 is preferred. The square calcined group is a group in which an aryl group is combined with fluorene. The calcined group is the same as the above-mentioned meaning. The aryl group has a carbon number of 5 to 12 as better than 0, and an inverse number of 6 to 8 is more preferable. The aryl group may be a heteroaromatic ring, and it is more preferable that it is formed from a hydrogen atom and a three oxygen, sulfur, or / and nitrogen atom. Can be substituted ", for example, a hydrocarbon group having a carbon number] to 20 (for example, a carbon number] to 6 ^, a hydrocarbon group such as an alkyl group, a ash number 5 to [2], etc. are preferred, Guardian child f 7 $ 巧 ^ 土) Shichang fire number] to 6 of the regular oxygen 'pixels, Jingji, Yu

U 313210D01 200410926 etc. In addition, the intermediary group can be alkylene, -0-, _s ... two-chain or split-like state and carbon number 1 to 6 2-or containing -〇-, -S〇- and carbon number 1 to 6 of alkylene.

The surface functional group may be a substituted hydrocarbon group having 1 to 20 carbon atoms, and is preferably represented by the following formula.

1 CH

, A has the same definition as above). ^ For example, 1 to 3 of the above-mentioned roasted glutamate = one or two sulphuroxy groups or / and 1 to 3 Kayoucan N + (CHJ ^ Yi Jia, and it is best to be substituted by 1 to 3 third butyl. Among 1 to 3, it is better to substitute by 2 substituents. In the invention, pure carbon or heterogen-containing double increase, specifically, such as surface functional groups, specifically, such as 筮 一 丁 曾 ^ NVpu, For example, di-dibutyl, CONH (CH2) 2 yCH3) 3, and methoxyloxy, etc. However, in the present invention, the third butyl group is preferred. The alkyl group may be straight-chain or branched, but a carbon number is preferred. Specifically, such as methyl, ethyl, n-propyl, isopropyl, or tert-butyl. Aralkyls such as fluorenyl and phenethyl. The alkoxy group may be straight-chain or branched, but a carbon number of C, · 4 is preferred, and specifically, such as fluorenyloxy, ethoxy, isopropoxy, or tertiary butoxy. The color-developing functional group may be a well-known color-developing functional group, and specifically, 313210D01 12 200410926, for example, from D-damin pigment, quinazoline, perylene, azo compound, 2,5-dihydroxybenzoin Acetic acid esters, oxoporphyrin, 4,4, dihydroxybiphenyl or 1- (4,4,4 "-trihydroxyphenyl) ethane-derived groups are preferred. (10) to (14) above Although the described synthetic intermediates are novel compounds, they can be easily manufactured industrially in accordance with reactions known per se. One of them is shown below. [Example] 313210D0] 200410926

Dendrimers can be produced using the synthetic intermediates obtained in this way. A reaction method known per se, for example, a divergent synthesis method of chemically synthesizing a dendritic structure from a core to an outer side toward a surface functional group, or a dendritic structure from an outermost surface functional group to an inner side Convergent synthesis methods for chemical synthesis toward the central core are all 313210D01 200410926. 0 In this way, the following compounds and dendrimers can be obtained.

313210D01 200410926 If the reaction of the above-mentioned production method is further carried out, for example, dendrimer compounds having a larger number of layers than the following can be obtained.

16 313210D01 200410926

Further, although the examples are used to illustrate the present invention, it should not be construed that the present invention is limited to these examples. The reaction of the examples is shown in the figure. Ex represents an example.

313210D0I 200410926

C02Me

CH2Br MeS 18 3132] 〇D01 200410926

〇 〇

19 313210D01 200410926 〇

h〇h2c

SH

SH

N ~ Me

—Me Me ’

Me

20 313210D01 200410926

21 3132I0D01 200410926

The following compounds were produced in the same manner as described above. 22 313210D01 200410926 MIMe f Me 、 NII i N 丨 Me Me

313210D01 200410926

24 313210D01 200410926

25 313210D01 200410926

3) 32) 0001 26 200410926

27 3132I0D01 200410926

28 313210D01 200410926

^ ^ Examples of the use of the compounds of the present invention will be specifically described with reference to the drawings. Fig. 1 is a schematic diagram showing the structure of a single Thai-core early hairy tunnel element according to the present invention. In the present invention, due to Shiji Tianwan, the lower electrode 2 on the substrate 1 and the lower 1 & Asian moon LB film layer 3 'middle electrode sound layer 4, the upper polyimide LB film 5 and the upper electrode 6 Laminate the covers in order. ^ ^ Constitutes an early electronic tunnel element. The material constituting the substrate 1 is not limited. For example, metal, ceramics, and plastic can be used as electronic component substrates. Both: lower electrode 2 and upper electrode can be used. In the Ben %% Ming, the so-called Juyabu & surname & two limbs are thoughtless by Lange Miao

， Polyimide 准 ° formed by quasi-jet method, 、 S female early knife 朕 or its accumulation film. Benfa, 313210D0] 29 200410926 A single electron tunnel element can be formed by accumulating the lower polyimide LB film layer 3 with 13 to 30 polyimide monomolecular films. As the polyimide constituting the polyimide LB film, various types of polyimide structures can be used. However, in the case of using a polyimide having a repeating unit represented by Formula 25, the thickness of the monomolecular film can be controlled. , So it is better. In this case, the formation of the polyimide LB film layer 3 is based on the accumulation of a monomolecular film under the polyacrylic acid state of the polyimide precursor moon bean, and then the imidization is performed by chemical treatment to good.

Then, on the lower polyimide LB film layer 3, a single-molecule layer of the polyimide LB film with dendrimer molecules of the present invention inserted is formed as the middle: electrode layer 4. It is expected that in order for the dendrimer molecules of the present invention to function as an interelectrode, the dendrimer molecules of the present invention must be used in a suitable polyimide LB film at an appropriate concentration (0.01 to 1%). On the intermediate electrode layer 4, the upper polyimide LB film '5 and the lower polyimide ⑶ film layer Η upper polyimide are formed in the same manner.

The Lb film layer 5 is composed of 20 to 30% flat and noisy 8-7 two-layer + I imine early molecular film accumulation. The upper polyimide LB film layer 5 is laminated on the upper electrode 6 to obtain the single _ rain master ― son tunnel element of the present invention. This single electron tunnel element forms an electron tunnel layer, due to the organic molecular characteristics of the lower poly I sublayer LB sublayer 3 and the upper polyisocyanate 31321OD01 30 200410926 amine lb film layer. 5 and the middle electrode layer 4 are entirely composed of materials, and can exhibit good early electron tunneling of f formed by the monoimine LB film

Manufacture of esters 5

A solution of 3,5-fluorenyl- (difluorenylaminofluorenylthio) benzyl acetate in acetic acid was added to anhydrous acetic acid, and 30 g of sodium methoxide was added dropwise in a nitrogen blanket. Then, the mixture was heated under reflux for i hours to make the reaction 'slightly cooled, and then an excess of sulfonium iodide was added, and the mixture was heated under reflux for 3 hours to make it react'. The residue obtained by concentration under reduced pressure was purified by chromatography. (Dilute with chloroform) to obtain the target compound. Yield 10.5 g (79.3 ° /.), Melting point 46 ° C. iH-NMR ((5ppm, CDC13, TMS); 2.5 (6Η, s), 3.9 (3H, s), 7.20H, s), 7.6 (2Η, s) Example 2 Via 3,5- Disulfanyl sulfonium system-sulfanyl sulfonium desert compound 31321000] 31 200410926

MeS

C02Me + NaAlH2 (OCH9CH0OMe)

MeS

MeS

CH0OH

MeS CBr4

Ph0P

MeS

CH2Br

MeS

Dissolve sodium dihydrofluorene (2-fluorenthoxyethoxy) aluminate (70% in methylbenzyl chloride, 0.17 mol) under nitrogen flow in anhydrous tetra AI: 5 to ^ drops of a sulfide Glycolic acid ~ ~ two o'clock. Will ::: solution. Then, the mixture was stirred at the same temperature, and ^ was added to a mixture of ^ ml of concentrated hydrochloric acid and ice water} liters, and 1 liter of chloroform was taken out. The extract was refined by gas imitation-the method was refined. Concentrated to dryness under reduced pressure, and washed with chromatographic petroleum to obtain 3,5_ dimethyl mercaptan, the residue of the material was used in -ml. Then add ~~ g ^^ PPh3 27 was added at the same time G.-Once the reaction solution becomes pale yellow, it will slowly precipitate white crystals (-pph3-0). After 20 to bright solution, the 'colorless crystals' will be removed after some time, and the concentrated residue will be reacted 3 Small series CHA ··· & = 1:! Dissolution) refined [to obtain two two = chromatography (to compounds. Yield 21.6 g (82%), melting point 76 to 7 ^ c. Thio T radical

Tetrahydropyran (shown elsewhere in the manual). THF Example i 313210D0] 32 200410926 Production of 3,5-fluorene- (3,5-difluorenylthiofluorenyl) via 3,5-fluorene- (3,5-difluorenylthiobenzyloxy) benzoic acid ethyl ester Benzyl alcohol

CH〇Br MeS

C〇2Me 18-crown-6

MeS

MeS

NaAlH2 (〇CH2CH2〇CH3) 2

MeS

21.0 g (0.080 mol) of 3,5-difluorenylthiofluorenyl desert, 6.7 g (0.040 mol) of phosphonium 3,5-dihydroxyphosphonate, and 28.0 g (0.20 mol) of potassium carbonate And 18-crown-6 2.1 grams (0.0080 mol) was added to 33 313210D01 200410926 5,000 strokes of water acetone 'heated to reflux in a nitrogen blanket] for one hour to make the reaction. The insoluble matter was removed from the reaction solution, and the filtrate was concentrated to dryness under reduced pressure. The extraction solution was purified by chromatography using chloroform as the developing solution. The residue was concentrated under reduced pressure to obtain methyl 3,5 (3 > dimethylthiobenzyloxy) acetate. It contains 21.0 grams (9 8.9%) and a melting point of 121 to 122 ° F. ΐ-NMILIK Qing, CDC13, TMS) · 2 "cut, 〇π ·"), 2.4S, S), 3 machines s), 4._, s), 6.3 square, hydrogen hydrazone (2methoxyethyl Oxy) sodium aluminate (70% in toluene, 22 7.8 g, 0.078 mole), in a nitrogen gas stream and under 5 to ⑽, dropwise ^, 5 to prepare (3 ^ dioxine sulfur Benzyloxy) acetic acid, vinegar, 210 gram > Gu Yu 180 liters of tetrahydrophosphine, Liu Lu ta 丨 Shi Fu Nan Zhi, the liquid. Then, the reaction mixture was stirred for 5 hours, And pour it into 2 liters of Zhao: ^ will ... Six A liters of dilute hydrochloric acid. Extract with 1 liter of chloroform. Concentrate the extraction solution to dryness under reduced pressure, weld, and use chloroform as the unfolding solution. & Purification by column chromatography to obtain 3,5 1-based) benzyl alcohol. Yield 17.5 g (85 · 6%). ^ yl alkoxy riurCDCl3 > ™ s): 2.402 ^ s) > 4.6 ^ s),, 5.1 Example 4 Manufacture of 3H (3,5_difluorenylthiobenzyloxy) benzyl filler 313210D01 34 200410926

17.0 g (0.033 mol) of 3,5-fluorene- (3,5-dimethylthiofluorenyloxy) benzyl alcohol and 14.2 g (0.043 mol) of carbon tetrabromide were dissolved in 100 ml of tetrahydrofuran Medium, and then a small amount of triphenylphosphine 11.3 g (0.043 mol) was added successively at 1.0 to 10 ° C. Then, the reaction solution was kept at the above temperature while being stirred for 7 hours. It was poured into 300 ml of ice water and extracted with chloroform. The extract was purified by chromatography to obtain 7.0 g of 3,5-fluorene- (3,5-difluorenylthiofluorenyloxy bromide. W-NMR (0 ppm, CDC13, TMS); 2.4 (12H , S), 4.4 (2H, s), 4.9 (4 Η, s), 6.5 to 7.1 (9 Η, m) Made

35 313210D0] 200410926 Put 3,5-dihydroxybenzyl acetic acid ester (168.2 g, mol), difluorenylthioamine fluorenyl chloride (280 · 4 · g, 2.2 Mol, purity 97%), potassium carbonate (300 g, 2.17 mol) and acetone (3,000 ml) were added to a 5-liter round bottom flask with a stirrer. The reaction mixture was reacted with stirring at 40 to 50 ° C for 24 hours. The reaction mixture was concentrated under reduced pressure to remove acetone, and cooled with an excess of water to obtain 3,5-fluorene-dimethylthiomocetomethoxymethoxyacetic acid methyl acetate as colorless crystals, which was recrystallized from ethanol to obtain 297.5 g (87% yield) of needle-like crystals. Melting point 132 to I ". LH-NMR (CDCl3); 3.34 (6H, s, Me x 2), 3.44 (6H, s, Me x 2), 3.90 (3H, s, Me), 7. 05-7. 09 (1H, m, ph-H), 7. 64-7. 67 (2H, s, ph-H)

Me represents CH3, and ph represents phenyl (the same applies in the description above and below). Example 6 Production of 3,5-fluorene-dimethylamine sulfanylbenzoic acid phosphonium ester

Methyl 3,5-fluorenyl-difluorenylthioamine oxoacetate (297.0 g, 0.867 mol) was added to sialylone (1.0 ml) at 210 to 213 ° C with stirring. The reaction was carried out under heating and refluxing for 3 hours. To this was added ethyl acetate (1000 ml), and it was washed with 5% cold sodium hydroxide aqueous solution (300 ml) and saturated brine (300 ml), and dried over magnesium thionite. 313210D01 36 200410926

After the deacetic acid was dehydrated, the residue was recrystallized from toluene (500 ml) to obtain colorless needle-like crystals of 3,5-dimethylamine formamidinethiobenzate. 219 g (74% yield). It has a melting point of 128 to 130. s, Me), 7.82 (1Η, S, ph-Η) 缶 NMR (CDC13); 3.05 (12Η, s, Mex4), 3.90 (3Η 8.17 (2s, s, ph-Η) Implementation Example 7 Production of 3,5-Dimercaptobenzyl phosphonium ester

, Ν—Me SH Me A solution of 3,5-dai-di-amidinoaminothiothioic acid (34 2 g, 0.100 mol) and 43 g of sodium methoxide in methanol (0.223 A mixture of Moore) and methanol (150 ml) was reacted at 22 to 25 t. After cooling with 500 ml of ice water, the reaction mixture was neutralized with concentrated hydrochloric acid to obtain colorless crystals. This was purified with methanol to obtain 12.5 g of 3,5-dimercaptobenzoate, a colorless powder (yield: 62.5%). Melting point 61 to 62. (: IH-NMR (CDC13); 3.51 (2Η, s, SH X 4), 3.87 (3Η, s, Me), 7.30 (1Η, t, J = 0.1 Hz, plHO , 8.67 (2H, d, J = 0.1 Hz, Ph-Η) Example 8 Production of 3 Dimercapto T-Acid Ethyl 37 313210D01 200410926

(Et means ethyl, the same applies hereinafter.) The above-mentioned reaction is carried out according to an ordinary esterification reaction to produce ethyl 3,5-dimercaptobenzoate. Melting point is 49 to 51 ° C.

] H-NMR (CDC13); 1.36 (3H, t, J = 0.02He, Me), 3.51 (2Η, s, SHx2), 4.33 (2Η, Q, CH2), 7.31 (1H, s, ph-H), 7.68 (2H, s, .ph-H) Furthermore, the free carboxylic acid 3,5-dimercaptobenzoic acid of the above-mentioned compound is in accordance with 3101 <: 〇, ~ .1 <[.; 811 (: 111 ^ 3] <:, 0.] \ 4 .; ya & 81 ^ 〇1, 31 < ^, 1 ^] \ 4 · Zh · 〇rg · Khim. (1 985), 21 ( 7), 1470-1477. Example 9 Production of 3,5-fluorenyl-difluorenylamine thiothiobenzoic acid

Mix 3,5-fluorenyl-difluorenylamine, phosphorothioate (3.42 g, 10 mol) and 5% aqueous sodium hydroxide (10 ml, 12.5 mmol) at 22 Allow to react to 25 ° C for 3 hours with stirring. The reaction mixture was cooled in 50 ml of ice water, extracted with ethyl acetate (300 ml × 3), and dried over magnesium sulfate. 313210D01 38 200410926 The reaction mixture was concentrated under reduced pressure, and ethyl acetate was distilled off to obtain colorless crystals. This was purified from ethanol to obtain 2.86 g (yield 87.2%) of 3,5-fluorenyl-dimethylaminoformylthiobenzoic acid as colorless needle crystals. Melting point 196 to 198 ° C (decomposed). Ή-NMR⑽S0-d6); 2.96 (6H, s, Me X 2), 3.03 (6H, s, Me X 2), 7.82 (1Η, s, Ph-H), 7.88 (lH, s, ph ~ H), 8.10 (1H, s, ph-H), 10.5 (1H, br-s, OH) Example 10 Manufacture of 3,5_wu-difluorenylaminosulfonic acid thiol alcohol

The 3,5-fluorene-dimethylaminoformamidinethiobenzylacetate (3.42 g, 10 mmol) dissolved in 20 ml of toluene was placed between 15 and 30. (: Added to sodium dihydrofluorene (2-oxoethoxy) aluminate (700 / 〇 in toluene, 8.7 g, 30.1 mmol), and reacted under stirring and heating under reflux for 3 hours The reaction mixture was cooled with 50 ml of ice water containing 10 liters of concentrated sulfuric acid, extracted with ethyl acetate (30 ml x 3), and the extract was dried over magnesium sulfate. The reaction mixture was concentrated under reduced pressure, and distilled After removing ethyl acetate, 2.54 g of a colorless oil was obtained. This was purified by column chromatography using chloroform as a dissolution solvent to obtain 3,5-dai-dimethyl as a colorless oil. Carbamidinethiobenzyl g, yield 38.5%). Α! Η-leg (CDC13); 2.9 coffee, s, Me χ 2), 2 94 (6H, s, heart χ 2), ugh 4.50 (2Η, s, CH2), 7.38 (2Η, s, ph-H), 7.44 (1Η, s, ph-H) '3] 32] 0D0] 39 200410926 Example 11 Production of 3,5-dimercaptobenzyl alcohol

N_Me decomposes 3,5-fluorenyl-difluorenylaminethiothiol by the usual method using sodium hydroxide to obtain 3 5 5 -diweilfluorenol. Example 1 Production of 2 3,5-Dimercaptofluorenylthiol

NaOH N-Me / Me

3,5-fluorenyl-difluorenylaminethiothiol is hydrolyzed by a conventional method using sodium hydroxide to obtain 3,5-dimercaptanol; brominated in the same manner as in Example 17, 3,5-Dimercaptobenzyl bromide is obtained; it is reacted with urea sulfide according to an ordinary method and then subjected to a decomposition reaction to obtain 3,5-dimercaptofluorenyl mercaptan. Example 1 Production of 3 3,5-fluorene-dimethylamine thioaniline 40 313210D01 200410926

NaN〇3 / HC!

O

The 3,5-fluoren-difluorenylamine thiosulfanyl T test amine was reacted with NaN03 / HCl according to a conventional method to obtain 3,5-fluoren-dimethylamine methylsulfanyl aniline. Example 14 Production of 3′-dimethylamine formamidinethiobenzidine

3,5-Diamino-dimethylaminomethylthiothiobenzoic acid (3.28 g, 10 mol) and thionine (30 mmol) were added to 30 ml of toluene. The compound was reacted under heating for 2 hours. After removing the excess sulfite donkey lice and acetophenone, the residue was poured into ammonia-ethanol (10%, 10 ml) to obtain 3,5 · dai-diamidomethylformamidinethione as colorless crystals. Stuffed amine. Melting point 264 to 265 ° C.

Ajjj column 15 Manufacture of 3,5, hydrazone- (3,5-di-tert-butylsulfenyl) benzoic acid 3I3210D01 41 200410926

-1-methyl 3,5-dimercaptobenzoate (20.0 g, 10.0 millimoles), 3 5-butyl fluorenyl bromide (57.0 g, 201.2 millimoles), 038 grams of 18-crown-6 (manufactured by Wako Pure Chemical Industries), calcium carbonate (28.0 grams, ears), and JL · 4 were added to 350 ml of acetone, and heated under reflux for 12 hours. Sowing, after a long period of time, the precipitated salt was removed, and then the acetone was removed. The residue was purified by column chromatography (solving with n-hexane: dichloromethane = 1: 1) to obtain 53 g of colorless needles. Crystalline 3,5-fluorene- (3,5-di-tert-butylbenzylthio) benzylformate. Melting point is 102 to 103 ° C.

Al ^ MlUCDCg; 1.29 (36H, S, Ter BiHI), 3.70 (3H, S, Me), 3.90 (4Η, S, SCH2), 7.10 (4Η, S, ph-Η), 7 · 29 (3Η, br-S, ph-H), 7.77 (12Η, S, ph-H) Example 1 3,5- 贰-(3-Di-tert-butyl〒thio) 〒 Manufacture of alcohol 42 313210D01 200410926

G, 86.0 mol) Soluble :) 甲 ^ a ^ (52.0 々 at the same time in dihydrocarb (2 P ㈣ and kept below 35 ° C gram, per millimol oxygen μ Lu acid steel After the 70% toluene solution was finished, the reaction solution was injected and stirred under the same conditions for 2 hours. After stirring for 1 minute, it was separated into 500 ml of a 10% hydrochloric acid solution, and then passed through a tube; Anhydrous sulfuric acid is used. Concentrated toluene. The viscous substance is prepared by di-dichloromethane (dichloromethane) and obtained as g-free gram. Diethyl dibutylsulfanyl) benzyl alcohol 4.96

MMR (CDC13); 1.42 (36H, S CH20), 7.23-7 · 26 (7Η mn: 丄 ⑴ BU ', 4.18 (4Η, S, S,>, 4.67 (2H, S, 7.42) (2Η, s, ph | Example 1 7 3,5 Preparation of (3,5'-di-third-butyl sulfanyl) sulfonium desert 313210D01 43 200410926

CH2Br M · 9 means hydrazone (3,5--tert-butylbenzylthio) T alcohol (49.0 g, hair, ear) and carbon tetrabromide (28.2 g, 85.0 (tetrahydro) Buffalo) in 300 ml, / valence 于 89 89 89 κ * * Triphenylphosphine (23.5 g, • pen mole) was added while stirring below 10 C. Once the reaction solution, μ a . t ^ stump transparent liquid is slower

: ,,… color crystals. Then, the reaction solution was decanted from 25 to 3 (the precipitated crystals were removed and concentrated. The residue was purified by column chromatography ^ hexane: dichloromethane = 1: 1 dissolution) 3,5-Yan (3,5-di-tertiary-butylbenzylthio) benzyl-desertide, which is a colorless viscous shell, 34.8 g, 0 tNMIUCDCg; 1.43 (36, S, tert-Bu -Η), 4.18 (4H s ca, t port ", 0, bUI2), 4 44 (2h 5 CH2Br), 7. 23-7. 25 (7H, m, ph ~ H),?. 43 (2H, S, ph-H) 'Example 18 Manufacture of dendrimer I 313210D01 44 200410926

Using 3,5-fluorene- (3,5-di-tert-butylbenzylthio) fluorenyl bromide (3 4.0 g, 5 3.1 mmol), the same method as in Example 15 was used to obtain 2 Dendrimer 1 (colorless, viscous substance) of 1.0 g of the target compound. MMRiCDCls); 1.28 (72H, S, tert-Βυ-Η), 3.76 (3H, S, Me), 3.89 (12H, S? SCH2), 7. 10 (12H, S, ph-H), 7.30 (7H , S, ph-H), 7.78 (2H, S, ph-H) Example 1 9 Manufacturing of dendrimer II 45 313210D01 200410926

Using dendrimer I (20.0 g, 15.17 mmol), in the same manner as in Example 16, 13.4 g of the target compound was obtained as a dendrimer Π (colorless viscous substance). • H-NMRCCDClg); 1.40 (72H, S, tert ~ Bu-H), 4.03 (12H, S, SCH2), 4.68 (2H, S, CH20), 7.09-7. 1 6 (1 2H, m, ph -H), 7.30 (7H, S, ph-H), 7.76 (2H, S, ph-H) 46 3J3210D01 200410926 Example 20 Manufacturing of dendrimer III

Using dendrimer II (13.0 g, 10.0 mmol), in the same manner as in Example 17, 6.7 g of the target compound dendrimer III was obtained as a colorless viscous substance.

47 313210D0I 200410926-NMR (CDC13); 1.40 (72Η, S, tert-Bu-H), 4.02 (12H, S, SCH2), 4.41 (2Η, S, CH2Br), 7.10-7.20 ( 12H, m, ph-H), 7.30 (7H, S, ph-H), 7.70 (2 Η, S, ph-H) Example 21 Manufacturing of dendrimers IV.

48 313210D01 200410926 Dendrimer iv was produced by the same reaction as in Example 18 using dendrimer III. That is, dendrimers ΙΠ, 6,8_dinitro-2, anal dimercaptoquinazoline, and L8-diazabicyclo (5,4, 〇) undec-7_ene are prepared in accordance with the usual method React in hydrogen D furan to produce dendrimers ιν. 22 Manufacture of 3,5 · Dimercaptobenzamine

The 3,5 -di-fluorenylamine thiothiobenzylamine was hydrolyzed by using a hydrogenated leather steel to produce 3,5 -diweilenic acid amine.

Manufacture of 3,5 · Dimercaptobenzamine Η2Ν

Me

3,5 ~ 贰 -Difluorenylamine and thioaniline are hydrolyzed by a conventional method using a gas% steel to produce 3,5-«-allylbenzylamine. < "Fonin 1 Column 24 Manufacture of 3,5-Dimercaptobenzonitrile 313210D01 49 200410926 / = (N_Me S- <

+ NaOH N a Me

SH

SH

Me decomposes 3, t 贰 -diamidylamine 曱 醯 thiobenzonitrile by a conventional method to hydrolyze sodium hydroxide aqueous solution to produce dimercaptobenzonitrile. Lice leather 1J & 1L25 Manufacture of methyl benzate

3,5-fluorene- (3 di-butyl fluorenyl bromide (molecular weight 28 soap, 57.0 g, 201.2 mormol) and potassium carbonate (molecular weight 138.21, 28 mol g, 202.0 mmol) Ear) ^ In 350 ml of propionate, the mixture was reacted under heating and refluxing; Γ After removing acetone and salts, the residue was burned with dichloromethane as a solution = cereal medium? Refined by tube decantation method ' Methyl 3,5-de ((5,1--second-butylsulfenyl) thio) acetate was obtained as acicular crystals. Multiple Example 26 3. Dimethylaminocarbonylthio-5-methylammonium methyl ester Made in 313210D01 50 200410926

HO

HO S f O One Me

In accordance with the procedures of Examples 5 and 6, using a half amount of dimethylthiomomidine chloride, the 3-dimethylthioaminoamidinyl-5-methylamino acid was converted from 3, Manufactured from methyl dihydroxyarsonate in 26% yield. Melting point is 135 to 138 ° C. 1H-NMR (CDC13); 3.0 & 3.05 (6Η, o.oovin, 〇rs, 〇H), 3.84 (3H, s, Me), 7.05, 7.47 & 7.78 (3H, s, s & s, Ph * H) Embodiment 27 FIGS. 2 to 4 are diagrams showing an example of a single-electron tunnel element according to the present invention. Fig. 2 is a plan view ', Fig. 3 is a ground view at the lamp line of Fig. 2, and Fig. 4 is a conceptual view of an enlarged joint portion of an element. The symbol 9 in the figure indicates the electron fluorene layer formed by the lower polyfluorene imine LB film layer 3, the interstitial electrode / and the upper fluorene imine LB film layer 5. s' substrate in electronic tracking device! Upper electrode and lower electrode Γ-The empty electrode is used to form an electrode with a thickness of ⑽ nanometers and no oxide film is formed. In addition, on the lower electrode 2, 3] 32] 〇D〇] 51 200410926 After accumulating 25 layers of polyimide LB film with T degree, i was imidized by chemical treatment to form lower polyimide LB.膜层 3。 Film layer 3. Then, the polyimide represented by the above-mentioned formula 25 and the dendrimer represented by the above-mentioned formula 24 are mixed so as to become 500: 1, and the dendrimer formed by the present invention is formed in the same manner as the lower poly-imide: B film layer 3. The body molecule is inserted into the intermediate electrode 4 formed by a single molecular layer of the polyimide LB film. From the molecular occupancy test, it can be seen that the area of the intermediate electrode 4 is about 1; the area of the angle ^ is larger than the compound of the above formula 24, and has an effective function as an intermediate electrode. Above the middle electrode layer 4 is the same as the lower polyimide M film layer 3 ::: Formula: After accumulating 30 layers of the polyimide LB film, the upper polyimide is formed by chemical treatment Amine LB film layer 5. Electrode 2: on the upper part of the upper polyimide ⑶ film layer 5 and the lower part of the electric a to make the upper part of the Au electrode formed by vacuum evaporation bell film thickness 50i 100nm and emulsified film The electrode 6 forms the preliminary electrode 7, and $, 丨 g σ is paid to the early-electron tunnel element. In this example, both the upper and lower electrodes 6 and 6 are preliminarily formed in order to compare the differences in the material characteristics of the present invention. To prevent the above, when the upper electrode 6 and the upper preliminary electrode 7 are made, the insulation of the edges of the lower electrode 2 is destroyed, and the lower polyimide M is formed from the middle electrode layer 4 and the upper polyimide is formed by the film layer 5. The defect lead 8 is formed by forming an edge coating layer covering the edge of the lower electrode 2 with this temple to make a device area of 50 × __ tunnel element. Early electron 313210D01 52 200410926 A single lower two & early bun tunneling element made of the compound of the present invention, because of the resistance of 22 and upper electrode 6 from several hundred MΩ to several tens 0Ω, measured by the two terminal method In a low-M thermostat, at a constant temperature, set v, and pen pressure 17, and measure the current with a galvanometer 18. The characteristic graph measured at the absolute temperature of 5 · 2K, although the A c% property is as shown in the figure of the younger brother. Although this port is at an extremely low temperature of 5.2K, it is a single electrical interval lightning-dissipation. The voltage equal to the characteristics of the tunnel element Π ~ According to the step of the early electron tunnel phenomenon < if the middle electrode 4 and the lower electrode 2 The amount of Ar, + 4 of the upper electrode 6 ... The amount of charge in the pen is e, then we can know that e / c becomes Λ _ ^ according to the < 5 m ^ r- voltage range. As shown in Figure 5, even though the voltage amplitude is 0 'mV ^ 1§... S ^, it is about 100 months once. _ Landlord's current electronic tunnel characteristics. Furthermore, "%" in this description means weight%, / The ratio of the media is the capacity ratio [effect of the invention] If the dendritic compound of the present invention is induced to emit light immediately upon being stimulated, it can be used as, for example, a memory structure: a thorn caused by 【[Schematic description of the structure] The purpose of the material is shown in Figure 1. Figure 1 shows the single electron tunnel of the present invention. Schematic diagram of the structure of 1,000 layers. Figure 2 shows the plane of an example of the single electronic tunnel element of the present invention. Figure 3 is the χχ line of Figure 2. Sectional view. Figure 4 is a conceptual diagram of the large joint of the component of Figure 2. Figure 5 is a single electric, sub-tunnel υ ~ L piece of the present invention presented at 5.2K] 313210D0] 53 200410926 Graphics.

1 Substrate 2 3 Lower polyimide LB film layer 4 5 Upper polyimide LB film layer 6 7 Upper preparation electrode 8 9 Electron tunnel layer 10 17 Step voltage 18 Lower electrode middle electrode layer Upper electrode edge coating single electron Tracking component ammeter

54 313210D01

Claims (1)

200410926 Scope of patent application: 1. A 3,5-dimercaptobenzyl alcohol. 2 · —Species 3 5 5 -diweikylamidine mercaptan. 3.-A species of methyl 3,5-fluorenyl-difluorenylaminothiobenzoate. 4. A methyl 3,5-difluorenylthiobenzoate. 5 · —Species 3,5 -diweikylide acid is cool. 6 · —Ethyl 3,5 -diweisyl gallate. 55 313210D01